CN1593917A - Ink-jet cloth printing ink and an ink-jet recording method - Google Patents

Ink-jet cloth printing ink and an ink-jet recording method Download PDF

Info

Publication number
CN1593917A
CN1593917A CNA200410077014XA CN200410077014A CN1593917A CN 1593917 A CN1593917 A CN 1593917A CN A200410077014X A CNA200410077014X A CN A200410077014XA CN 200410077014 A CN200410077014 A CN 200410077014A CN 1593917 A CN1593917 A CN 1593917A
Authority
CN
China
Prior art keywords
ink
printing ink
jet
cloth
cloth printing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CNA200410077014XA
Other languages
Chinese (zh)
Other versions
CN100408332C (en
Inventor
森本仁士
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Konica Minolta Inc
Original Assignee
Konica Minolta Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2003320895A external-priority patent/JP2005089498A/en
Priority claimed from JP2003324259A external-priority patent/JP4552408B2/en
Application filed by Konica Minolta Inc filed Critical Konica Minolta Inc
Publication of CN1593917A publication Critical patent/CN1593917A/en
Application granted granted Critical
Publication of CN100408332C publication Critical patent/CN100408332C/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
    • D06P5/30—Ink jet printing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B67/00—Influencing the physical, e.g. the dyeing or printing properties of dyestuffs without chemical reactions, e.g. by treating with solvents grinding or grinding assistants, coating of pigments or dyes; Process features in the making of dyestuff preparations; Dyestuff preparations of a special physical nature, e.g. tablets, films
    • C09B67/0071—Process features in the making of dyestuff preparations; Dehydrating agents; Dispersing agents; Dustfree compositions
    • C09B67/008—Preparations of disperse dyes or solvent dyes
    • C09B67/0082—Preparations of disperse dyes or solvent dyes in liquid form
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
    • D06P3/00—Special processes of dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form, classified according to the material treated
    • D06P3/34—Material containing ester groups
    • D06P3/52—Polyesters
    • D06P3/54—Polyesters using dispersed dyestuffs

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Coloring (AREA)

Abstract

The invention relates to a kind of spraying printing ink, comprised of decentralized dyestuff, dispersing agent, water and water soluble organic solvent, of which the common radius of the decentralized dyestuff is 100nm to 300nm, the solubility of the dyestuff is 10-5 to 10-3 g.

Description

Ink-jet cloth printing ink and ink jet recording method
Technical field
The present invention relates to ink-jet cloth printing ink and the ink jet recording method that uses it.
Background technology
In field of printing and dyeing, as the coping style of shortening delivery date, a small amount of many variety production, preferred ink-jet cloth printing mode.Dyeing for fibers such as polyester, usually use disperse dyes, but when disperse dyes are used for the ink-jet time spent, except as printing and dyeing in the past with the performances such as the tone of dye selection benchmark, fastness, because ink-jet recording is for to spue from fine nozzle, therefore exist and be used to the restriction that makes its dispersion adaptability that becomes minuteness particle, prevent nozzle mesh obstruction, dispersion stabilization etc., many to the restriction of dye selection.In addition, exist in recording ink in ink-jet and not allow oversize grain etc. that the fine nozzle mesh that spues is blocked, the rerum natura of printing ink does not change and solid constituent such as does not separate out at problem in the manufacturing or in preserving.Particularly be the printing ink of colouring agent with disperse dyes, because it is scattered in dispersion in the aqueous medium for colorant particles, the oversize grain that contains in the printing ink is except small dust etc., the colorant particle macroparticle that aggegation forms in the preservation process that also comprises dispersion, with compare easier generation oversize grain for the dye ink of perfect solution.Open in the clear 64-48875 communique the spy, put down in writing by filtering in manufacturing process and centrifugation, the mesh that will become nozzle blocks and solid constituent is separated out the method that oversize grain is removed in the printing ink of reason.
In addition, also proposed to make pigment stably to be scattered in various motions in the ink composite.For example, proposed utilization in the special public clear 55-35434 communique and had the dispersant of the polymer of lipophile part and hydrophilic parts as dispersed color.In addition, special fair 4-5703 communique has proposed to use the dispersant of the polymer of lipophile part with particular range molecular weight and hydrophilic parts as dispersed color.
For disperse dyes printing ink, adopt the method for when making oversize grain being removed, can't obtain sufficient stability, even adopt the method identical to make the kind optimization of surfactant, dispersant etc., also can't solve fully with pigment.
In addition, on the other hand, contained molten resolution and the distinctiveness that gas is its printed article of infringement of depositing causes the main cause that micro air bubble produces in the printing ink, blocks because of it produces mesh sometimes.Open in the flat 10-298470 communique the spy, put down in writing printing ink is passed through in the hollow-fibre membrane with gas-premeable, the outer surface side decompression by to hollow-fibre membrane makes the molten method of depositing gas permeation, removing in the printing ink.But these methods can not also be difficult to fully bubble be removed even adopt the above-mentioned degassing to handle in disperse dyes printing ink to all printing ink performance effect of sufficient.
In light of this situation, the invention provides the ink-jet cloth printing ink of ejection, excellent storage stability.
Summary of the invention
Above-mentioned problem of the present invention is reached by following formation.
(1), ink-jet cloth printing ink, it contains disperse dyes, dispersant, water, water-miscible organic solvent at least, it is characterized in that: the average grain diameter of disperse dyes be 100nm above, below the 300nm, colorant dissolubility is 10 in the printing ink -5G is above, 10 -3Below the g.
(2), (1) record ink-jet cloth printing ink, it is characterized in that: above-mentioned colorant dissolubility is 10 -5G is above, 10 -4Below the g.
(3), the ink-jet cloth printing ink of (1) or (2) record, it is characterized in that: also contain polyvalent metal, the total content of described polyvalent metal is 1ppm～1000ppm, above-mentioned disperse dyes have the structure that can form chelate with above-mentioned polyvalent metal.
(4), (3) record ink-jet cloth printing ink, it is characterized in that: the total content of above-mentioned polyvalent metal is 10ppm～1000ppm.
(5), (4) record ink-jet cloth printing ink, it is characterized in that: the total content of above-mentioned polyvalent metal is 100ppm～1000ppm.
(6), the ink-jet cloth printing ink of each record of (3)～(5), it is characterized in that: above-mentioned polyvalent metal is to be selected from Ca, Mg, Ti, Al, Zn, Fe, Co, Ni and Cu at least a kind.
(7), the ink-jet cloth printing ink of each record of (1)～(6), it is characterized in that: use hollow fiber film assembly to outgas.
(8), ink jet recording method, it is characterized in that: using nozzle diameter is that the following ink gun of 30 μ m sprays the ink-jet cloth printing ink of each record of above-mentioned (1)～(7).
(9), ink jet recording method, it is characterized in that: use driving frequency to spray the ink-jet cloth printing ink of each record of above-mentioned (1)～(7) as the ink gun more than the 20kHz.
(10), ink jet recording method, it is characterized in that: use ink jet speed to spray the ink-jet cloth printing ink of each record of above-mentioned (1)～(7) as the ink gun more than the 6m/s.
(11), ink jet recording method, it is characterized in that: the ink-jet cloth printing ink of each record of above-mentioned (1)～(7) is ejected on the cloth and silk that contains polyester fiber.
(12), ink jet recording method, it is characterized in that: to use nozzle diameter be the following ink gun of 30 μ m is ejected into the ink-jet cloth printing ink of each record of above-mentioned (1)～(7) on the cloth and silk that contains polyester fiber.
According to above-mentioned formation, can obtain that mesh blocks or precipitation less, ink-jet cloth printing ink that stability is high, use this ink-jet cloth printing ink, can carry out high meticulous ink mist recording, printing and dyeing.
Specific embodiments
Below optimum implementation of the present invention is elaborated, but the present invention is not limited to these schemes.
The result that present inventors study with keen determination particularly in will carrying out the ink-jet cloth printing ink that water system disperses as the dispersed color of colouring agent, with concentrating on to have on the feature of disperse dyes of utmost point low solubility, has carried out significantly keeping quality improvement.
Disperse dyes being separated into particulate printing and dyeing with in the jetted ink, require the good stability of dispersion, do not produce the particle precipitation, do not make obstructions such as nozzle and filter.
In the ink-jet cloth printing ink that has used disperse dyes, recognize for the keeping quality and the stability of dispersed particle being had great influence as the dissolubility of the water of disperse dyes medium or water-miscible organic solvent, surfactant, dispersant.
Disperse dyes are insoluble in water, but have some to have dissolubility.If particularly particle diameter reduces, then solubility increases.That is, recognize if particle diameter distribute wide, small-particle dissolving and separating out on macroparticle in the preservation, i.e. crystalline growth, particle diameter increases gradually, produces that mesh blocks or precipitation.In addition, crystalline growth speed is arranged by the solubility of dyestuff.That is, greatly then crystalline growth speed is big for solubility, and the little then crystalline growth of solubility speed is little.
Therefore, big to a certain degree and have in the disperse dyes printing ink that particle diameter distributes in solubility, in any case can produce crystalline growth, generate oversize grain.
On the other hand, in the printing ink of disperse system, be difficult to bubble is removed fully.For the dissolving of having used water soluble dyestuffs is printing ink, for example, even use hollow fiber film assembly to outgas easily, but for the disperse system printing ink that solid dispersed is used in water system, sometimes even be difficult to remove fully attached to the bubble of the surface of solids with said method.In this case, can't outgas fully, owing to the cavitation erosion produces the injection bad.
Present inventors carry out found that of various researchs, and in the low ink formulations of colorant dissolubility, because the compatibility of solvent, dispersant and colorant particle is low, so wetability is poor, in this case bubble is removed fully difficulty especially.
The present inventor finds, is adjusted in certain scope by the solubility with dyestuff in the printing ink, can suppress crystalline growth, and make it have enough wetabilitys, outgases easily.That is, if the colorant dissolubility height blocks because crystalline growth produces mesh,, then be difficult to outgas fully ejection aspect existing problems if colorant dissolubility is low.Therefore, in ink formulations, 2 opposite problems can be solved simultaneously with certain colorant dissolubility.
In addition, colorant dissolubility is by the total surface area decision of solids, and is in the scope of particle diameter more than 100nm, below the 300nm, effective for above-mentioned problem.That is, if be the particle diameter of this scope, because the crystalline growth that the difference of colorant dissolubility produces is few, in addition, the adhesion amount of dye particles blibbing is also few, and the effect of the above-mentioned degassing is also big.
Therefore, with the involved in the present invention ink-jet cloth printing ink of disperse dyes microparticulate in water and/or water-miscible organic solvent, when the average grain diameter of disperse dyes is more than the 100nm, below the 300nm, the colorant dissolubility in the printing ink is 10 -5More than, 10 -3During following scope, ink-jet cloth printing ink can not block because of crystalline growth produces mesh, and in addition, bubble is also few at the adhesion amount of particle surface, and the effect of the degassing is big.Colorant dissolubility more preferably 10 -5More than, 10 -4Following scope.
On the other hand, in order to improve wetability, if the colorant dissolubility design is high, because disperse dyes have the solubility of trace, small-particle dissolving and on macroparticle, separating out in preservation, i.e. crystalline growth, particle diameter increases gradually, produces that mesh blocks or precipitation.In addition, crystalline growth speed is by the solubility decision of dyestuff.That is, if solubility greatly then crystalline growth speed is big, the little then crystalline growth of solubility speed is little.
The result of present inventor research finds to slow down in order to make its crystalline growth speed in the printing ink with sufficient dyestuff wetability, and it is effective adding polyvalent metal in having used the printing ink with disperse dyes that can chelate structure.
In the present invention, the mensuration of colorant dissolubility is carried out according to following method in the printing ink.
Except not adding the dyestuff, adopt with the identical composition of printing ink and make solubility test liquid, in this solubility test liquid, add 0.1% dyestuff powder, carry out stirring in 5 hours (25 ℃).After stirring end, with whizzer undissolved dyestuff is all precipitated, the dissolving part that taking-up is clarified above.Adopt HPLC that the top concentration of clarifying the dyestuff of part that is present in this dyestuff dissolving is carried out quantitatively.As normally used, solubility is the solute amount (g) of every 100g solution.
In addition, ink-jet cloth printing ink of the present invention has only when containing polyvalent metal, except not adding dyestuff and polyvalent metal, adopts with the identical composition of printing ink and carries out same mensuration.
In addition, there is no particular restriction for HPLC, for example, can use Inert Sil ODS-2 (anti-phase silica) as post, appropriate change is formed use 0.1M ammonium acetate buffer (pH5), methyl alcohol etc. as elutriant, measures by UV detector (for example detecting wavelength is 260nm).
Especially, be used for the printing ink of printing machine etc., what contain in the printing ink moltenly deposits resolution or the distinctiveness that gas becomes its printed article of infringement, causes the main cause that micro air bubble produces.
As from printing ink with molten method of depositing the gas degassing, comprise utilizing and boil or method that physical method such as decompression outgases and make absorbent sneak into chemical method in the printing ink etc.Can outgas with any means, but in the present invention, by printing ink is passed through in the hollow-fibre membrane with gas-premeable, thereby make the molten method of depositing gas permeation, removing in the printing ink can not produce harmful effect the outer surface side decompression of hollow-fibre membrane to the rerum natura of printing ink, and can effectively the molten gas of depositing in the printing ink be removed, therefore preferred.Particularly when the average grain diameter of disperse dyes was above-mentioned scope (more than the 50nm, below the 300nm), degasifying effect was good.
Average grain diameter can be tried to achieve by the commercially available particle size determination machine that has used light scattering method, electrophoresis, laser Doppler method etc.As concrete particle size determination device, for example can enumerating, マ Le バ one Application society makes ゼ one one サ イ ザ 1 etc.
In addition, also preferably use ultrasonic generator (for example, the UH-600S of SMT society, 20kHz, 600W) etc. that printing ink is carried out that ultrasonic wave is handled and the method for the degassing etc.In addition, state hollow-fibre membrane when degassing decompression in the use, ultrasonic generator for example also preferably is installed and the method that will carry out the method combination that ultrasonic wave handles in the printing ink stream.According to this method, the printing ink flow velocity when changing the degassing can be adjusted the degassing degree of printing ink, is adjusted into the required molten air capacity of depositing.
In the present invention, by carrying out above-mentioned degassing operation, the preferred molten air concentration of depositing reaches below the 30ppm.The more preferably molten air concentration of depositing is below the 20ppm, is 20ppm～0ppm.
The molten air concentration of depositing can be measured dissolved oxygen concentration, is that the basis is obtained with the ratio of oxygen in the air.
Dissolved oxygen concentration can adopt Ostwald (Ostwald) method (experimental chemistry lecture 1 basic operation [1], 241 pages, 1975, ball are kind) or mass spectrometric determination, can adopt easy oxymeter such as galvanic cell type or polarogram type or colorimetric analysis to measure.
In addition, dissolved oxygen concentration can use commercially available dissolved oxygen concentration meter, and for example mensuration such as DO-30A type are made in East Asia electric wave industry (strain).The molten air concentration of depositing is by measuring dissolved oxygen concentration and obtaining based on the ratio of oxygen in the air.
In order to obtain high meticulous image, preferably use the ink gun of nozzle diameter 10 μ m～50 μ m to carry out record.From graininess, below the preferred 50 μ m, because the too small meeting of droplet size is subjected to the influence of air-flow, therefore more than the preferred 10 μ m.
The printing ink that the present invention relates to, excellent in stability, thick disperse dyes particle is few, and nozzle diameter is little, is the printing ink of suitable droplet ink-vapo(u)r recording.Ink-jet cloth printing ink involved in the present invention in above-mentioned 10 μ m～50 μ m, uses below the nozzle diameter 30 μ m, and further the following ink gun of preferred 20 μ m can not produce the mesh obstruction of ink gun or spray bad, therefore preferred especially when spraying.
In addition, ink-jet cloth printing ink involved in the present invention can be more than the 20kHz with driving frequency, further is used in combination for the above ink gun of 30kHz.
In addition, for ink jet speed, can be more than the 6m/s with it, more preferably ink jet speed is that the above ink gun of 8m/s is used in combination, and can stably use.
As mentioned above, used nozzle structure that disperse dyes printing ink can't stabilized driving, shower nozzle drive condition etc. even use, ink-jet cloth printing ink involved in the present invention can obtain enough ejections in the past.
Dyeing method involved in the present invention on color development efficient, more preferably uses ink-jet cloth printing ink involved in the present invention, adopts ink-jet method containing record on the cloth and silk of polyester fiber.
As the raw material that constitute the cloth and silk that uses in the dyeing method of the present invention, as long as contain the fiber that can use disperse dyeing, there is no particular restriction, wherein preferably contains fibers such as polyester, acetate, triacetate.Wherein, the cloth and silk that especially preferably contains poly-vinegar fiber at least.As cloth and silk, can make the above-mentioned fiber of enumerating is any forms such as fabric, volume thing, nonwoven.In addition, as the cloth and silk that uses among the present invention, can be 100% with the fiber of disperse dyeing preferably, but also can use the blending of artificial silk, silk floss, polyurethane, acrylic compounds, nylon, wool and thin,tough silk etc. weave cotton cloth or blending nonwoven etc. as the printing and dyeing cloth and silk.In addition, as the thickness of the fiber that constitutes above-mentioned various cloth and silk, the scope of preferred 10～100d.
Dyeing method involved in the present invention is to adopt ink-jet method that ink-jet cloth printing ink involved in the present invention is ejected on the cloth and silk that contains polyester fiber.
Under the situation of ink jet printing method involved in the present invention, in order to obtain the product dyed thereby of homogeneous, preferably before cloth and silk being carried out pre-treatment, the residual component (sizing material etc.) of the medicament that uses in the natural impurity (grease, wax, pectic substance, natural colouring matter etc.) that adheres on the cloth and silk fiber, the cloth and silk manufacture process, dirt etc. are washed with the water soluble polymer class.The washing agent that uses during as washing can use NaOH, the such alkali of sodium carbonate, anionic surfactant, the such surfactant of nonionic surface active agent, enzyme etc.
In dyeing method involved in the present invention,, preferably use pad dyeing method, rubbing method, spray-on process etc. to give pretreating reagent (pretreatment procedure) for bleeding prevents effect.Then, use the printing ink of above-mentioned formation on the cloth and silk of the fiber that contains the enough disperse dyeings of energy, to form image (printing ink gives operation) with ink-jet recording, then the cloth and silk that has given printing ink is heat-treated (color development operation), and then will carry out heat treated cloth and silk washing (washing procedure), thereby finish printing and dyeing, obtain dyeing material cloth and silk.
As pre-treatment, can from cloth and silk is carried out known methods such as pre-treatment with the water soluble polymer class, suitably choose the method that is suitable for fiber raw material and printing ink, be not particularly limited.For example, if the cloth and silk that has given at least a kind of material that 0.2～50 quality % is selected from water-soluble metal salt, polycationic compounds, water soluble polymer, surfactant and waterproofing agent is used, bleeding can be prevented to heavens, high meticulous image can be on cloth and silk, printed, therefore preferred.
Below enumerate the example of the concrete water soluble polymer that is used for pre-treatment.As water-soluble macromolecule, can use starch based such as corn, wheat, cellulose derivatives such as carboxymethyl cellulose, methylcellulose, hydroxyethylcellulose, polysaccharides such as sodium alginate, グ ア one ガ system, tamarind gum, locust bean gum, gum arabic, protein materials such as gelatin, casein, keratin; As the synthesizing water-solubility macromolecule, can use polyvinyl alcohol, polyvinylpyrrolidone, acrylic polymer etc.As surfactant, for example can use anionic, cationic, both sexes, nonionic surface active agent, the sulfonate of higher alcohol sulfate salt, bitter edible plant derivative etc. as anionic surfactant, can be enumerated in representative ground; As cationic surface active agent, can enumerate quaternary ammonium salt etc.; As amphoteric surfactant, can enumerate imidazolidine derivatives etc.; As non-ionic surface active agent, can enumerate the ethylene oxide adduct of polyoxyethylene alkyl ether, polyoxyethylene propylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, alkynol etc.In addition, as waterproofing agent, for example can enumerating, silicon, fluorine system and wax are material.These are administered to water soluble polymer or surfactant on the cloth and silk in advance, are carrying out ink jet printing, when at high temperature making its color development, do not become owing to tarring causes dirt in order to make it, and are preferably stable for hot environment.In addition, these are administered to water soluble polymer or surfactant on the cloth and silk in advance, are carrying out ink jet printing, at high temperature make in the carrying out washing treatment behind its color development, preferably remove from cloth and silk easily.
The cloth and silk of lettering batches after the ink jet printing method that carries out lettering on the cloth and silk is preferably with ink jet, makes its color development by heating, and cloth and silk is washed and make its drying.In ink-jet cloth printing, can not dye well if behind printing ink lettering on the cloth and silk, just place.In addition, when long cloth and silk is carried out the long-time continuous lettering, because cloth and silk constantly exports, go up and occupy the place thereby the cloth and silk of lettering overlaps floor etc., this is dangerous and produce the dirt that not have expectation sometimes.Therefore, behind lettering, need to batch operation.When this is operated, can between cloth and silk and cloth and silk, sandwich paper or cloth, vinylite etc. and the irrelevant medium of lettering.But, when cutting off or for short cloth and silk, then needn't batch midway.
Because printing back is only attached to the cloth and silk surface, the color development operation is fully to adsorb, dyestuff absorption in the fixing printing ink, be fixed on the cloth and silk by making not by cloth and silk, thereby embodies the operation of the original form and aspect of this printing ink.As its method, can utilize the steaming baking of adopting steam, adopt the baking of heating, the pad-dry-cure dyeing method, adopt superheated steam the HT steam generator, adopt the HP steam generator of steam under pressure etc.These methods can suitably be selected according to the raw material that print, printing ink etc.In addition, can carry out heat treated immediately, carry out heat treated after also can placing a little while the cloth and silk of lettering, according to purposes carry out drying, color development is handled, and in the present invention, can use any method.
When using disperse dyeing, be not only the method that makes its color development under the high temperature, can use carrier.The compound that uses as carrier preferably has following feature: dyeing, it is big to promote, using method is easy, stable, and is little to the load of human body and environment, removes simply from fiber, do not influence colorfastness.As the example of carrier, can enumerate the such phenols of o-phenyl phenol, p-phenyl phenol, the methyl bitter edible plant, benzoic acid alkyl ester, alkyl salicylate, chlorobenzene, biphenyl, ethers, organic acid, hydro carbons etc.These materials promote the swelling and the plasticization of the difficult dyeability fiber of dyeing difficulty under the temperature about 100 ℃ as polyester, and disperse dyes are entered in the fiber easily.The cloth and silk fiber that carrier is adsorbed onto in advance be used for ink jet printing also can make it be contained in the jetted ink.
Need washing procedure after the heat treated.This is to have and the first dyestuff that closes of dyeing, the bad stability of color, fastness reduction because of residual.In addition, also need the pre-treatment thing that is implemented on cloth and silk is removed.If do not remove, then not only fastness reduces but also the cloth and silk variable color.Therefore, must carry out and remove object and the corresponding washing of purpose.Its method is selected according to raw material, the printing ink of printing, for example, when being polyester, uses the mixed liquor of caustic soda, surfactant, bisulfites to handle usually.This method therefore in the present invention, can be used any method usually with continuous type such as open soaper or adopt the batch-type of liquid-flow dyeing machine etc. to implement.
Must carry out drying after the washing.After the crowded press for extracting juice of the cloth and silk of washing, dehydration, dry or use drying machine, hot-rolling, flatiron etc. to make its drying.
Disperse dyes in the ink-jet cloth printing ink of the present invention are not for having the nonionic dyestuff of sulfonic acid, carboxyl isoiony water soluble group.Be scattered in the water by dispersant, be used for the dyeing of synthetic fibers.Disperse dyes are different from pigment, dissolve in the organic solvents such as acetone or dimethyl formamide.In addition, to synthetic fibre staining the time, be diffused in the fiber with molecularity.
These disperse dyes are that exploitation is used as acetic ester fiber at first, and it is many with the needs of dyestuff as polyester fiber now.Polyester is compared with dyestuff with acetate with dyestuff, selection hydrophobic deg, the dispersion fuel that hear resistance is high.The parent of disperse dyes uses monoazo class, amino anthracene quinones, the more micromolecular parent of diphenylamine.
In the present invention, as preferred disperse dyes, can enumerate:
C.I. disperse yellow 3,4, and 5,7,9,13,23,24,30,33,34,42,44,49,50,51,54,56,58,60,63,64,66,68,71,74,76,79,82,83,85,86,88,90,91,93,98,99,100,104,108,114,116,118,119,122,124,126,135,140,141,149,160,162,163,164,165,179,180,182,183,184,186,192,198,199,202,204,210,211,215,216,218,224,227,231,232;
C.I. disperse orange 1,3, and 5,7,11,13,17,20,21,25,29,30,31,32,33,37,38,42,43,44,45,46,47,48,49,50,53,54,55,56,57,58,59,61,66,71,73,76,78,80,89,90,91,93,96,97,119,127,130,139,142;
C.I. Red-1 200,4,5,7,11,12,13,15,17,27,43,44,50,52,53,54,55,56,58,59,60,65,72,73,74,75,76,78,81,82,86,88,90,91,92,93,96,103,105,106,107,108,110,111,113,117,118,121,122,126,127,128,131,132,134,135,137,143,145,146,151,152,153,154,157,159,164,167,169,177,179,181,183,184,185,188,189,190,191,192,200,201,202,203,205,206,207,210,221,224,225,227,229,239,240,257,258,277,278,279,281,288,298,302,303,310,311,312,320,324,328;
C.I. disperse violet 1,4, and 8,23,26,27,28,31,33,35,36,38,40,43,46,48,50,51,52,56,57,59,61,63,69,77;
C.I. Disperse Green 9;
C.I. disperse brown 1,2, and 4,9,13,19;
C.I. disperse blue 3,7, and 9,14,16,19,20,26,27,35,43,44,54,55,56,58,60,62,64,71,72,73,75,79,81,82,83,87,91,93,94,95,96,102,106,108,112,113,115,118,120,122,125,128,130,139,141,142,143,146,148,149,153,154,158,165,167,171,173,174,176,181,183,185,186,187,189,197,198,200,201,205,207,211,214,224,225,257,259,267,268,270,284,285,287,288,291,293,295,297,301,315,330,333;
C.I. disperse black 1,3,10,24 etc.
In addition, when ink-jet cloth printing ink of the present invention contains polyvalent metal, preferably have the structure that can form coordinate bond, specifically, preferably in dye molecule, have the structure shown in chemical formula (1)～(13) with polyvalent metal.
Figure A20041007701400131
(in the formula, R represents hydrogen or alkyl).
As can be used in the disperse dyes that can form the coordinate bond structure that have of the present invention, in the commercially available product of having stated, can enumerate with polyvalent metal:
C.I. disperse yellow 4,5, and 8,16,60,82;
C.I. disperse orange 29;
C.I. Red-1 200 5,141,210;
C.I. disperse violet 1,4,6;
C.I. Disperse Green 1;
C.I. disperse blue 3,7,15,20,22,23,26,34,35,79,125,165,183 etc., but be not particularly limited to these dyestuffs.
In the present invention, as mentioned above, in ink-jet cloth printing ink, in order to make colorant dissolubility in the printing ink, the solubility that promptly constitutes dyestuff in the medium of this distributes ink system is 10 -3(g) following, 10 -5(g) Yi Shang scope is selected above-mentioned disperse dyes or is constituted other components of printing ink, and the average grain diameter of disperse dyes is adjusted to scope more than the 100nm, below the 300nm.
The solubility of dyestuff can be adjusted with the kind or the amount of the kind of employed organic solvent or amount, dispersant.Disperse particle diameter the end dispersion to adjust when requiring the time point of particle diameter when reaching.
In the printing and dyeing of having used disperse dyes, when using high-temperature process to make its color development, become the reason of pollution, the disperse dyes that the fastness that preferably distils is good to the white ground of machinery or fabricbase in order not make dye sublimation.
As the content of disperse dyes, preferred 0.1～20 quality %, more preferably 0.2～13 quality %.
Disperse dyes can directly use commercially available product, but preferably carry out refinement treatment.As process for purification, can use known recrystallization method, washing etc.The organic solvent that is used for process for purification and refinement treatment is preferably suitably chosen according to the kind of dyestuff.
Polyvalent metal involved in the present invention is preferably at least a kind that is selected from Ca, Mg, Ti, Al, Zn, Fe, Co, Ni and Cu.
Polyvalent metal involved in the present invention preferably adds with the form of multivalent metal salt.Anion is not particularly limited, and for example, can use chloride, sulfide, hydroxide etc.Can use and organic salt, in addition, can be for adding the oxide that the back is decomposed, dissolved.
Concrete polyvalent metal compounds is as follows, but is not particularly limited in these salt.
Can enumerate for example calcium chloride, calcium acetate, calcium oxide, magnesium chloride, magnesium fluoride, magnesium acetate, magnesium bromide, magnesium formate, magnesium nitrate, magnesium sulfate, titanium chloride, titanium iodide, aluminium chloride, aluminium oxide, aluminium bromide, silver iodide, aluminum sulfate, aluminum nitrate, zinc chloride, zinc bromide, iron chloride, cobalt chloride, nickel chloride, copper chloride etc.Wherein, the preferred chloride of each polyvalent metal.
As water-miscible organic solvent of the present invention, (for example for example can enumerate polyalcohols, ethylene glycol, glycerine, 2-ethyl-2-(methylol)-1, ammediol, tetraethylene glycol, triethylene glycol, tripropylene glycol, 1,2, the 4-butantriol, diethylene glycol (DEG), propane diols, DPG, butanediol, 1, the 6-hexylene glycol, 1, the 2-hexylene glycol, 1, the 5-pentanediol, 1, the 2-pentanediol, 2,2-dimethyl-1, ammediol, 2-methyl-2, the 4-pentanediol, the 3-methyl isophthalic acid, the 5-pentanediol, the 3-methyl isophthalic acid, the 3-butanediol, the 2-methyl isophthalic acid, ammediol etc.), amine (monoethanolamine for example, 2-(dimethylamino) ethanol etc.), unary alcohol (methyl alcohol for example, ethanol, butanols etc.), the alkyl ether of polyalcohol (diethylene glycol monomethyl ether for example, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether, the triethylene glycol monobutyl ether, glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether etc.), 2,2 '-dihydroxy diethyl sulfide, amide-type (for example N, dinethylformamide etc.), heterocyclic (for example 2-Pyrrolidone etc.), acetonitrile etc.
As the water-miscible organic solvent amount, be 10～60 quality % preferably with respect to the printing ink gross mass.
For the viscosity that keeps printing ink or dyestuff is stable and make color development good, can in printing ink, add inorganic salts.As inorganic salts, can enumerate for example sodium chloride, sodium sulphate, magnesium chloride, magnesium sulfide etc.When enforcement is of the present invention, be not limited to these inorganic salts.
As surfactant, can use any of cationic, anionic, both sexes, nonionic.As cationic surface active agent, can enumerate aliphatic amine salt, aliphatic quaternary ammonium salt, zephiran salt, benzethonium chloride, pyridiniujm, imidazole salts etc.As anionic surfactant, can enumerate fatty acid soaps; N-acyl group-sarcosine salt; N-acyl group-N-methyl-Beta-alanine salt; the N-acyl glutamate; alkylether sulfonate; the acyl group peptide; alkylsulfonate; alkylbenzenesulfonate; alkyl bitter edible plant sulfonate; the dialkyl sulfosuccinate succinate salt; alkyl sulfoacetate; alpha-alkene sulfonate; the N-acyl methyl N-taurate; sulfonated oil; higher alcohol sulfate salt; senior secondary alcohol sulfuric acid; alkyl ether sulfate; senior secondary alcohol ethoxy sulfate; polyoxyethylene alkylphenyl ether sulfate salt; monoglyceride sulfate; the fatty acid alkyl alcohol amide sulfuric acid; alkyl ether phosphate salt; alkyl phosphate salt etc.As amphoteric surfactant, can enumerate carboxybetaine type, sulfobetaines type, aminocarboxylate, imidazoles betaine etc.As nonionic surface active agent, can enumerate polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkyl phenyl ether (for example エ マ Le ゲ Application 911), polyoxyethylene sterol ether, the Wool wax alcohols,ethoxylated derivative, polyoxyethylene polyoxy-propylene (for example ニ ユ one Port one Le PE-62), the polyoxyethylene fatty acid glyceride, Emulsifier EL-60, hardened castor oil, polyoxyethylene sorbitan fatty acid ester, the polyoxyethylene sorbitol fatty acid ester, cithrol, fatty acid monoglyceride, polyglyceryl fatty acid ester, sorbitan fatty acid ester, methyl glycol fatty acid ester, sucrose fatty ester, fatty acid alkanol amides, the polyoxyethylene fatty acid acid amides, polyoxyethylene alkyl amine, alkyl amine oxide, acetylenediol, acetylene alcohol etc.The present invention is not limited to these materials.
When using these surfactants, can use separately or use, preferably add the surfactant of 0.001～1.0 quality % scope, thereby can at random adjust the surface tension of printing ink with respect to total ink with mixing more than 2 kinds.
In order to keep the long preservation stability of printing ink, can in printing ink, add anticorrisive agent, mould inhibitor.As anticorrisive agent, mould inhibitor, can enumerate aromatic halide (for example Preventol CMK), methylene dithiocyanogen hydrochlorate, halogen-containing nitrogen sulfur compound, 1,2-benzisothiazole-3-ketone (for example PROXEL GXL) etc.The present invention is not limited to these materials.
The printing ink that uses among the present invention when being water-insoluble dyestuff, can use dispersion machine to disperse dyestuff, dispersant, wetting agent, medium and additive mixing arbitrarily.As dispersion machine, can use known in the past ball mill, sand mill, line grinding machine, high-pressure homogenizer etc.
As the particle diameter of disperse dyes, average grain diameter can be adjusted to below the 300nm scope that 100nm is above, 300nm is following.If average grain diameter, maximum particle diameter are big, from the printing ink dyeing method of fine nozzle ejection, be easy to generate mesh and block, can not stablize injection.Average grain diameter can be tried to achieve by the commercially available particle size determination machine that has used light scattering method, electrophoresis, laser Doppler method etc.As concrete particle size determination device, for example can enumerating, マ Le バ one Application society makes ゼ one one サ イ ザ 1 etc.
Dispersant prevents aggegation between the dispersed solids particulate in the medium, for making the compound of stably dispersing, can use low molecular surfactant or macromolecule dispersing agent.
The preferred dispersant that uses can be enumerated for example formalin condensation product of creasote sodium sulfonate (for example デ モ one Le C) among the present invention, the formalin condensation product of cresol sulfonic acid sodium and 2-naphthol-6-sodium sulfonate, the formalin condensation product of cresol sulfonic acid sodium, the formalin condensation product of sodium phenolsulfonate, the formalin condensation product of β-naphthol sodium sulfonate, the formalin condensation product of β-bitter edible plant sodium sulfonate (for example デ モ one Le N) and β-naphthol sodium sulfonate, ligninsulfonate (for example バ ニ レ Star Network ス RN), alkane sulfonate (for example エ Off コ one Le 214), the copolymer of alpha-olefin and maleic anhydride (for example Off ロ one レ Application G-700) etc.
The use amount of dispersant is with respect to preferred 20～200 quality % of disperse dyes.If dispersant is few, then micronize and dispersion stabilization are poor, if dispersant is many, micronize and dispersion stabilization are poor, and viscosity increased is therefore not preferred.These dispersants can use separately, also can and use.
Preferred humectants during the present invention disperses is neopelex, 2-ethylhexyl sodium sulfosuccinate, alkyl bitter edible plant sodium sulfonate, the ethylene oxide adduct of phenol, the ethylene oxide adduct of acetylenediol etc.
Because the structure of the disperse dyes that use, make and produce foaming, gelation or mobile variation in the dispersion, except wetting power, particlized ability and dispersion stabilization, consider the foaming when disperseing, the gelation of dispersion liquid, the flowability of dispersion liquid etc., must choose dispersant and wetting agent.In addition, consider when making its color development under the influence of generations such as the dyeability to cloth and silk, the distinctness that is dying rate, level-dyeing property, migration property, color, fastness and the high temperature because the tarring of dispersant and wetting agent, dyeing becomes inhomogeneous etc., preferably chooses dispersant and wetting agent.Owing to do not satisfy the dispersant of above-mentioned requirements fully, therefore, select optimal dispersant according to the dyestuff that disperses, must add defoamer etc. as required.
Preferably, the printing and dyeing of using when dyeing with high temperature steaming method are with containing the auxiliary agent of having illicit sexual relations in the cloth and silk that uses in jetted ink or the printing and dyeing printing.Dye auxiliary agent when the steaming dyeing cloth, having the eutectic mixture that forms with condensing water in the cloth shape, suppressing moisture evaporated amount again, shortening the effect of heating-up time.In addition, this eutectic mixture has the dyestuff on the dissolving fiber, the effect that improves the diffusion velocity of dyestuff on fiber.As dying auxiliary agent, can enumerate urea.
Embodiment
Below in conjunction with embodiment the present invention is specifically described, but the present invention is not limited to these embodiment.
Embodiment 1
(mensuration of colorant dissolubility in the printing ink)
Except not adding the dyestuff, to make solubility test liquid with the identical composition of printing ink.In this solubility test liquid, add dyestuff powder 0.1%, carry out stirring in 5 hours.After stirring end, with whizzer undissolved dyestuff is all precipitated, the dissolving part that taking-up is clarified above.Adopt HPLC that the top concentration of clarifying the dyestuff of part that is present in this dyestuff dissolving is carried out quantitatively.As normally used, solubility is the solute amount (g) of every 100g solution.
The HPLC determinator
Degasser: the system Degassing unit Model 546B of GL Science society
Pump: the system Intelligent Pump L-6200 of Hitachi
Post gas stove: ガ ス Network ロ industry system
Detector: the system UV-vis Detector L-4200 of Hitachi
Integrator: the system GPC Integrater D-2520 of Hitachi
Sampler: the system Intelligent Auto Sampler AS-4000 of Hitachi
Condition determination:
Post: Inert Sil ODS-2 (anti-phase silica) 4.6mm ID * 205mml
Stove: 40 ℃
Flow: 0.8ml/min
Injection volume: 20 μ l
The composition of elutriant: elutriant A before 20 minutes: elutriant B=30: elutriant A: elutriant B=0: 100 after 7020 minutes
Elutriant A:0.1M ammonium acetate buffer pH5
Elutriant B: methyl alcohol
Detect wavelength: 260nm
(dispersion liquid 1)
Use sand mill that following mixed liquor is disperseed.When arriving 200nm, average grain diameter stops to disperse.
C.I. disperse yellow is 149 25 parts
25 parts of glycerine
25 parts of ion exchange waters
25 parts of wooden sodium sulfonates
(バ ニ レ Star Network ス RN this system paper (strain) system)
Average grain diameter uses the system ゼ one one サ イ ザ 1 of マ Le バ one Application society to measure.
＜printing ink 1 〉
Then following component is mixed, filter with 3 μ m molecular filters, the processing that outgases obtains printing ink 1.
1 50 parts of dispersion liquids
40 parts of ethylene glycol
0 part of glycerine
0.01 part of プ ロ キ セ Le GXL (S)
(ア PVC シ ア Zhu Shi commercial firm system)
11 parts of Off ロ one レ Application G-700 (common prosperity society chemistry system)
The ion exchange water remnants of defeated troops
Off ロ one レ Application G-700 neutralizes with the NaOH of necessary amount in advance.
Identical with printing ink 1, the composition that uses dispersion liquid 1 to press table 1 is made printing ink 2～5.
In addition, after the printing ink of modulation outgases by the following method, carry out vacuum and fill.
Make printing ink by in the hollow-fibre membrane (mitsubishi rayon's system) with gas-premeable, reduce pressure, the molten gas of depositing in the printing ink is removed with the outer surface side of current aspirator to hollow-fibre membrane.In addition, the printing ink flow velocity when outgasing by changing makes dissolved oxygen concentration reach 2ppm.
Dissolved oxygen concentration uses the dissolved oxygen concentration meter of selling on the market (East Asia electric wave industry (strain) system DO-30A type), measures under 25 ℃, 1 atmospheric pressure.In addition, average grain diameter is same as described above, uses the system ゼ one one サ イ ザ 1 of マ Le バ one Application society to measure.
Table 1
Dispersion liquid Ethylene glycol Glycerine プロキセル Off ロ one レ Application Remarks
Printing ink 1 50 parts 40 parts - 0.01 part 11 parts Comparative example
Printing ink 2 50 parts 40 parts - 0.01 part 7 parts The present invention
Printing ink 3 50 parts 40 parts - 0.01 part - The present invention
Printing ink 4 50 parts 16 parts 20 parts 0.01 part - The present invention
Printing ink 5 50 parts 10 parts 23 parts 0.01 part - Comparative example
プ ロ キ セ Le: PROXEL GXL (1, the 2-benzisothiazole-3-ketone)
Off ロ one レ Application: Off ロ one レ Application G-700 (common prosperity society chemistry system)
For the solubility of dyestuff in each ink formulations, also measure as stated above.
[filter filtration test]
With the printing ink 2L that makes 40 ℃ preserved for 4 weeks after, make it pass through wire gauze filter (#3500 order, 10 Φ), when investigation has or not mesh to stop up, filter surfaces is observed with electron microscope.
A: no 2L mesh stops up, and does not have the surplus of crystallizing into electron microscope observation
B: no 2L mesh stops up, and crystallizes into surplus with electron microscope observation
C: between 1～2L, produce mesh and stop up
D: below 1L, produce mesh and stop up
[ejection estimates 1]
Use the piezo-electric type shower nozzle of nozzle diameter 40 μ m, driving frequency 10kHz, nozzle number 64, spray and estimate ejection.Adjust driving voltage so that jet velocity is 6m/s.
The stable injection
Under 25 ℃, the environment of relative humidity 50%, each printing ink 500ml of continuous injection, according to following metewand to the bending that before printing ink does not have, produces with owe to inject the row evaluation.
A: whole nozzle ejection
B: produce bending at 1～3 nozzle place, find to owe to penetrate
C: produce bending at 4～7 nozzle places, find to owe to penetrate
D: produce bending at the nozzle place more than 8, find to owe to penetrate
[ejection estimates 2]
Except using the piezo-electric type shower nozzle of nozzle diameter 30 μ m, driving frequency 20kHz, nozzle number 64, adjust driving voltage so that liquid drop speed is outside the 8m/s, estimate 1 identical the evaluation with ejection.
[ejection estimates 3]
Except using the piezo-electric type shower nozzle of nozzle diameter 20 μ m, driving frequency 30kHz, nozzle number 64, adjust driving voltage so that liquid drop speed is outside the 8m/s, estimate 1 identical the evaluation with ejection.
Evaluation result is as follows.
Table 2
Solubility Filtration test Ejection estimates 1 Ejection estimates 2 Ejection estimates 3 Average grain diameter Remarks
Printing ink 1 ??1.5×10 -3 ??D ??A ??A ??A ??200nm Comparative example
Printing ink 2 ??1.0×10 -3 ??B ??B ??B ??B ??200nm The present invention
Printing ink 3 ??1.0×10 -4 ??B ??B ??B ??B ??200nm The present invention
Printing ink 4 ??1.0×10 -5 ??A ??B ??B ??B ??200nm The present invention
Printing ink 5 ??0.8×10 -5 ??A ??D ??D ??D ??200nm The present invention
Can see that printing ink of the present invention compares with comparative example printing ink, more excellent in filtration test and ejection are estimated.
Embodiment 2
Adopt the prescription identical with dispersion liquid 1, the time point that reaches 350nm, 300nm, 100nm, 80nm in average grain diameter respectively stops dispersion, prepares dispersion liquid 2～5.
Use dispersion liquid 2～5, adopt the prescription identical, making printing ink 6～9 with printing ink 3.In addition, behind printing ink to manufacture, measure average grain diameter.
For the printing ink of making, identical with embodiment 1, use the piezo-electric type shower nozzle to carry out ejection and estimate 1, and printing ink is carried out the filter filtration test.
Table 3
Filtration test Ejection estimates 1 Average grain diameter
Printing ink 6 ????D ??B ????80nm
Printing ink 7 ????B ??B ????100nm
Printing ink 8 ????B ??B ????300nm
Printing ink 9 ????D ??D ????350nm
Printing ink involved in the present invention filter filtration test, ejection estimate two aspect excellence.
Embodiment 3
" modulation of printing ink "
(dispersion liquid-11)
Use sand mill that following mixed liquor is disperseed.When reaching 200nm, average grain diameter stops to disperse.
C.I. disperse yellow is 149 25 parts
20 parts of glycerine
25 parts of ion exchange waters
25 parts of wooden sodium sulfonates
(バ ニ レ Star Network ス RN Nippon Paper (strain) system)
(printing ink-11)
Then following component is mixed, filter with 3 μ m molecular filters, the processing that outgases obtains printing ink-11.
Dispersion liquid-11 50 part
48 parts of ethylene glycol
0.01 part of プ ロ キ セ Le GXL (S)
(ア PVC シ ア Zhu Shi commercial firm system)
Calcium chloride (addition is in the calcium component) 0.1ppm
The ion exchange water remnants of defeated troops
(dispersion liquid-12)
Use sand mill that following mixed liquor is disperseed.When reaching 200nm, average grain diameter stops to disperse.
C.I. disperse blue 60 is 25 parts
20 parts of glycerine
25 parts of ion exchange waters
25 parts of wooden sodium sulfonates
(バ ニ レ Star Network ス RN Nippon Paper (strain) system)
(printing ink-12)
Then following component is mixed, filter with 3 μ m molecular filters, the processing that outgases obtains printing ink-12.
Dispersion liquid-12 50 part
48 parts of ethylene glycol
2.5 parts of Off ロ one レ Application G-700 (common prosperity society chemistry system)
0.01 part of プ ロ キ セ Le GXL (S)
(ア PVC シ ア Zhu Shi commercial firm system)
Calcium chloride (addition is in the calcium component) 10000ppm
The ion exchange water remainder
In addition, Off ロ one レ Application G-700 neutralizes with the NaOH of necessary amount in advance.
Similarly press the composition of table 4 and make printing ink 13～16.
In addition, the printing ink that makes adjustment reduces pressure with the outer surface side of current aspirator to hollow-fibre membrane by in the hollow-fibre membrane (mitsubishi rayon's system) with gas-premeable, and the molten gas of depositing in the printing ink is removed.
In addition, adopt the determination method identical that colorant dissolubility in each ink formulations is measured with embodiment 1.In addition, when when containing the printing ink of polyvalent metal, under the state that does not contain polyvalent metal, measure.
Table 4
Printing ink No. Dispersion liquid Ethylene glycol プロキセル Off ロ one レ Application Calcium chloride Solubility Remarks
???11 50 parts 48 parts 0.01 part ??- ??0.1ppm ??5×10 -5 The present invention
???12 50 parts 40 parts 0.01 part 2.5 part ??10000ppm ??5×10 -5 The present invention
???13 50 parts 40 parts 0.01 part 2.5 part ??- ??5×10 -5 The present invention
???14 50 parts 40 parts 0.01 part 2.5 part ??100ppm ??5×10 -5 The present invention
???15 50 parts 40 parts 0.01 part 2.5 part ??10ppm ??5×10 -5 The present invention
???16 50 parts 40 parts 0.01 part 2.5 part ??1000ppm ??5×10 -5 The present invention
Each printing ink for making carries out following evaluation.
" evaluation "
(crystalline growth test)
After preserving 1 week, 2 weeks, under 40 ℃, use electron microscope to amplify 20,000 times and respectively the particle shape of the printing ink made is observed.When the rod-shaped particle more than the discovery 500nm, judge to exist to crystallize into surplus.
B: nothing crystallizes into surplus
C: the particle of finding 300nm～500nm
D: crystallize into surplus
(tackify test)
Similarly under 40 ℃, after preserving for 2 weeks, use the viscometer determining ink viscosity.Ratio of viscosities after just having made with printing ink when viscosity rising 0.5mPas is above, has been judged as tackify.
B: no tackify
C: the viscosity of finding 0.3mPas～0.5mPas rises
D: tackify is arranged
Crystalline growth test, tackify test the results are shown in following table 5.
Table 5
Printing ink No. The crystalline growth test The tackify test Remarks
1 week 2 weeks
????11 ????C ????C ????B The present invention
????12 ????B ????B ????C The present invention
????13 ????C ????C ????B The present invention
????14 ????B ????B ????B The present invention
????15 ????B ????B ????B The present invention
????16 ????B ????B ????B The present invention
In printing ink of the present invention, the concentration that can see polyvalent metal is the extraneous printing ink of 1～100ppm, and is poor in crystalline growth test and tackify test part omitted.
Embodiment 4
Replace the calcium chloride of printing ink 12 among the embodiment 3 and use the polyvalent metal compounds shown in the following table 6, similarly modulate printing ink 21～28.
Table 6
Printing ink No. Multivalent metal salt Multivalent metal salt Solubility Remarks
Kind Addition Kind Addition
????21 Zinc chloride 100ppm ??- ??- 5×10 -5 The present invention
????22 Aluminium chloride 100ppm ??- ??- 5×10 -5 The present invention
????23 Copper chloride 100ppm ??- ??- 5×10 -5 The present invention
????24 Nickel chloride 100ppm ??- ??- 5×10 -5 The present invention
????25 Iron chloride 100ppm ??- ??- 5×10 -5 The present invention
????26 Cobalt chloride 100ppm ??- ??- 5×10 -5 The present invention
????27 Calcium chloride 50ppm Zinc chloride ??50ppm 5×10 -5 The present invention
????28 Calcium chloride 50ppm Iron chloride ??50ppm 5×10 -5 The present invention
Use the printing ink of above-mentioned adjustment to carry out the evaluation identical, the results are shown in following table 7 with embodiment 3.
Table 7
Printing ink No. The crystalline growth test The tackify test Ejection is estimated Remarks
1 week 2 weeks Ejection estimates 1 Ejection estimates 2
??21 ??B ??B ??B ????B ????B The present invention
??22 ??B ??B ??B ????B ????B The present invention
??23 ??B ??B ??B ????B ????B The present invention
??24 ??B ??B ??B ????B ????B The present invention
??25 ??B ??B ??B ????B ????B The present invention
??26 ??B ??B ??B ????B ????B The present invention
??27 ??B ??B ??B ????B ????B The present invention
??28 ??B ??B ??B ????B ????B The present invention
Can see that each characteristic of printing ink of the present invention is all excellent.
Embodiment 5
Use the printing ink of making among the embodiment 3, use the piezo-electric type shower nozzle of nozzle diameter 20 μ m, driving frequency 30kHz, nozzle number 64, adjust driving voltage so that liquid drop speed is 8m/s, carry out ink-jet cloth printing on the cloth and silk of polyester fiber containing, used ink-jet cloth printing ink of the present invention, its printing image color height, and anti-oozing property is also excellent.In addition, no problem generation on ejection in long-term ink-jet cloth printing.

Claims (12)

1. ink-jet cloth printing ink, it contains disperse dyes, dispersant, water, water-miscible organic solvent at least, and wherein the average grain diameter of disperse dyes is 100nm～300nm, and colorant dissolubility is 10 in the printing ink -5～10 -3G.
2. the described ink-jet cloth printing ink of claim 1, wherein said colorant dissolubility is 10 -5～10 -4G.
3. the described ink-jet cloth printing ink of claim 1 wherein also contains polyvalent metal, and the total content of described polyvalent metal is 1ppm～1000ppm, and above-mentioned disperse dyes have the structure that can form chelate with above-mentioned polyvalent metal.
4. the described ink-jet cloth printing ink of claim 3, wherein the total content of above-mentioned polyvalent metal is 10ppm～1000ppm.
5. the described ink-jet cloth printing ink of claim 3, wherein the total content of above-mentioned polyvalent metal is 100ppm～1000ppm.
6. the described ink-jet cloth printing ink of claim 3, wherein above-mentioned polyvalent metal are to be selected from Ca, Mg, Ti, Al, Zn, Fe, Co, Ni and Cu at least a kind.
7. the described ink-jet cloth printing ink of claim 1 wherein uses hollow fiber film assembly that printing ink is outgased.
8. ink jet recording method, it comprises following operation: using nozzle diameter is that the following ink gun of 30 μ m sprays the described ink-jet cloth printing inks of claim 1.
9. ink jet recording method, it comprises following operation: using driving frequency is that the ink gun more than the 20kHz sprays the described ink-jet cloth printing ink of claim 1.
10. ink jet recording method, it comprises following operation: using ink jet speed is that the ink gun more than the 6m/s sprays the described ink-jet cloth printing ink of claim 1.
11. ink jet recording method, it comprises following operation: the described ink-jet cloth printing ink of claim 1 is ejected on the cloth and silk that contains polyester fiber.
12. ink jet recording method, it comprises following operation: using nozzle diameter is that the following ink gun of 30 μ m is ejected into the described ink-jet cloth printing ink of claim 1 on the cloth and silk that contains polyester fiber.
CNB200410077014XA 2003-09-12 2004-09-09 Ink-jet cloth printing ink and an ink-jet recording method Expired - Lifetime CN100408332C (en)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2003320895A JP2005089498A (en) 2003-09-12 2003-09-12 Inkjet printing ink and inkjet recording method
JP320895/2003 2003-09-12
JP2003324259A JP4552408B2 (en) 2003-09-17 2003-09-17 Ink jet textile printing ink, ink jet recording method and ink jet textile printing method
JP324259/2003 2003-09-17

Publications (2)

Publication Number Publication Date
CN1593917A true CN1593917A (en) 2005-03-16
CN100408332C CN100408332C (en) 2008-08-06

Family

ID=34138027

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB200410077014XA Expired - Lifetime CN100408332C (en) 2003-09-12 2004-09-09 Ink-jet cloth printing ink and an ink-jet recording method

Country Status (3)

Country Link
US (1) US7344236B2 (en)
EP (1) EP1514969B1 (en)
CN (1) CN100408332C (en)

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102190931A (en) * 2010-03-16 2011-09-21 精工爱普生株式会社 Ink composition and recording method
CN102341543A (en) * 2009-03-05 2012-02-01 柯尼卡美能达喷墨技术株式会社 Ink-Jet Textile Printing/Recording Process
CN101864206B (en) * 2009-04-16 2012-09-05 明德国际仓储贸易(上海)有限公司 Digital textile ink composition
CN102850844A (en) * 2011-06-28 2013-01-02 富士胶片株式会社 Ink composition, ink container, and ink jet recording method
US8530412B2 (en) 2005-03-30 2013-09-10 Canon Kabushiki Kaisha Ejection liquid, ejection method, method of making droplets from liquid, cartridge and ejection device
CN104194381A (en) * 2014-08-13 2014-12-10 东华大学 Crosslinkable active disperse dye compound as well as preparation method and application thereof
CN104245337A (en) * 2012-04-26 2014-12-24 惠普发展公司，有限责任合伙企业 Fabric print media
CN105733356A (en) * 2009-12-22 2016-07-06 科旺 Ink for printing on molded parts, and method for using said ink
CN106189511A (en) * 2016-08-30 2016-12-07 广东丽格科技股份有限公司 A kind of quick-drying digital jet ink of high concentration and preparation method thereof
CN109487578A (en) * 2018-12-04 2019-03-19 深圳市墨库图文技术有限公司 Thief zone heat sublimation ink and preparation method thereof

Families Citing this family (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7344236B2 (en) 2003-09-12 2008-03-18 Konica-Minolta Holdings, Inc. Ink-jet cloth printing ink and an ink-jet recording method
JP2005281523A (en) * 2004-03-30 2005-10-13 Konica Minolta Holdings Inc Manufacturing method of inkjet ink and inkjet recording method
PL2451648T3 (en) 2009-07-10 2015-05-29 Sawgrass Tech Inc High viscosity heat sensitive ink printing process
US8485657B2 (en) * 2010-01-08 2013-07-16 Advanced Chemical Solutions, Llc Sublimation printing processes and fabric pretreatment compositions for ink jet printing onto arbitrary fabrics
CN102924960B (en) * 2012-11-29 2014-04-23 南京大学 Benzo isothiazole azo pyrazolone disperse dye as well as preparation method and use thereof
US9085161B2 (en) 2013-06-07 2015-07-21 Electronics For Imaging, Inc. Systems, structures and associated processes for inline ultrasonication of ink for printing
JP6041152B2 (en) * 2013-11-13 2016-12-07 セイコーエプソン株式会社 Inkjet ink composition for sublimation transfer, ink set, and method for producing dyed product
CN106320031A (en) * 2015-06-29 2017-01-11 东莞市新美诺数码印花技术有限公司 Aqueous nylon fabric dye sublimation ink for gravure printing machine and preparation technology thereof
CN106320030A (en) * 2015-06-29 2017-01-11 东莞市新美诺数码印花技术有限公司 Aqueous nylon fabric dye sublimation ink for color printing machine and preparation technology thereof
US10676626B2 (en) 2016-09-27 2020-06-09 Seiko Epson Corporation Ink jet textile printing ink composition and ink receiving container
WO2018112030A2 (en) * 2016-12-13 2018-06-21 Ecc See Level Innovation Llc New processes for photo real embroidery technology for garments in sustainable and eco-friendly ways
CN111040509A (en) * 2020-01-06 2020-04-21 丁玉玲 LDP leather-like ink

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5410023A (en) 1977-06-22 1979-01-25 Dainichiseika Color Chem Aqueous ink composition for writing instrument
DE3683683D1 (en) * 1985-05-21 1992-03-12 Canon Kk INK-JET PRINTING METHOD.
JPH02276874A (en) 1990-02-26 1990-11-13 Canon Inc Ink jet recording of on-demand type
JPH06145568A (en) 1992-07-27 1994-05-24 Kanebo Ltd Ink for ink jet printing
JP3761940B2 (en) * 1994-10-28 2006-03-29 キヤノン株式会社 Inkjet printing ink, inkjet printing method, transfer textile printing method, printed matter, recording unit, ink cartridge, inkjet recording apparatus, and processed product
JPH09291235A (en) 1996-04-26 1997-11-11 Canon Inc Aqueous dispersion ink for ink jet printing and ink jet recording device using the same
JPH10114865A (en) 1996-10-11 1998-05-06 Canon Inc Aqueous microdispersion of disperse dye, disperse dye ink containing the same and used for ink jet recording and method for dyeing cloth with the same
JPH10298470A (en) 1997-04-30 1998-11-10 Mitsubishi Rayon Co Ltd Method and apparatus for deaerating ink
EP1174476B1 (en) * 2000-06-21 2004-09-01 Seiko Epson Corporation Aqueous ink
JP3874336B2 (en) * 2000-12-05 2007-01-31 株式会社リコー Recording liquid, ink jet recording method using the same, and recording apparatus
GB0102974D0 (en) 2001-02-07 2001-03-21 Avecia Ltd Dispersions
JP4154899B2 (en) 2002-02-21 2008-09-24 コニカミノルタホールディングス株式会社 Inkjet image recording method
US7344236B2 (en) 2003-09-12 2008-03-18 Konica-Minolta Holdings, Inc. Ink-jet cloth printing ink and an ink-jet recording method

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8530412B2 (en) 2005-03-30 2013-09-10 Canon Kabushiki Kaisha Ejection liquid, ejection method, method of making droplets from liquid, cartridge and ejection device
CN102341543B (en) * 2009-03-05 2013-04-24 柯尼卡美能达喷墨技术株式会社 Ink-jet printing and dyeing recording process
CN102341543A (en) * 2009-03-05 2012-02-01 柯尼卡美能达喷墨技术株式会社 Ink-Jet Textile Printing/Recording Process
CN101864206B (en) * 2009-04-16 2012-09-05 明德国际仓储贸易(上海)有限公司 Digital textile ink composition
CN105733356A (en) * 2009-12-22 2016-07-06 科旺 Ink for printing on molded parts, and method for using said ink
CN105733356B (en) * 2009-12-22 2019-01-29 Ivy集团控股 Ink for being printed on mechanograph and the method using the ink
US9321267B2 (en) 2010-03-16 2016-04-26 Seiko Epson Corporation Ink composition and recording method
US8820906B2 (en) 2010-03-16 2014-09-02 Seiko Epson Corporation Ink composition and recording method
CN102190931B (en) * 2010-03-16 2014-10-29 精工爱普生株式会社 Ink composition and recording method
US9120309B2 (en) 2010-03-16 2015-09-01 Seiko Epson Corporation Ink composition and recording method
US9855742B2 (en) 2010-03-16 2018-01-02 Seiko Epson Corporation Ink composition and recording method
CN102190931A (en) * 2010-03-16 2011-09-21 精工爱普生株式会社 Ink composition and recording method
CN102850844A (en) * 2011-06-28 2013-01-02 富士胶片株式会社 Ink composition, ink container, and ink jet recording method
CN102850844B (en) * 2011-06-28 2016-04-06 富士胶片株式会社 Ink composite, ink reservoir and ink jet recording method
CN104245337A (en) * 2012-04-26 2014-12-24 惠普发展公司，有限责任合伙企业 Fabric print media
CN104245337B (en) * 2012-04-26 2017-05-03 惠普发展公司，有限责任合伙企业 Fabric print media
US9193206B2 (en) 2012-04-26 2015-11-24 Hewlett-Packard Development Company, L.P. Fabric print media
CN105086509A (en) * 2014-08-13 2015-11-25 东华大学 Crosslinkable reactive disperse dye compound and preparation and application thereof
CN104194381B (en) * 2014-08-13 2017-01-11 东华大学 Crosslinkable active disperse dye compound as well as preparation method and application thereof
CN105086509B (en) * 2014-08-13 2017-10-03 东华大学 A kind of cross-linking reactive disperse dyes compound and its preparation and application
CN104194381A (en) * 2014-08-13 2014-12-10 东华大学 Crosslinkable active disperse dye compound as well as preparation method and application thereof
CN106189511A (en) * 2016-08-30 2016-12-07 广东丽格科技股份有限公司 A kind of quick-drying digital jet ink of high concentration and preparation method thereof
CN109487578A (en) * 2018-12-04 2019-03-19 深圳市墨库图文技术有限公司 Thief zone heat sublimation ink and preparation method thereof

Also Published As

Publication number Publication date
CN100408332C (en) 2008-08-06
US20050057631A1 (en) 2005-03-17
EP1514969B1 (en) 2011-11-30
US7344236B2 (en) 2008-03-18
EP1514969A1 (en) 2005-03-16

Similar Documents

Publication Publication Date Title
CN1593917A (en) Ink-jet cloth printing ink and an ink-jet recording method
CN1249180C (en) Printing ink, ink box, recording unit, ink-jet recording method, apparatus and stabilizing method
CN1084815C (en) Ink-jet printing process and print
CN1095009C (en) Printing process, ink set for use in such process, and print and processed article obtained thereby
CN1130433C (en) Jet ink and process for preparing dispersion of colored fine particles for jet ink
CN1049712C (en) Ink jet printing method and printed article
CN1140666C (en) Process for printing textile fibre materials in accordance with ink-jet printing process
CN1232062A (en) Mottle improvement in aqueous pigmented ink jet inks
CN101050326A (en) Ink jet recording ink, recording method and recording apparatus
CN1854210A (en) Microencapsulated particulate metal material, method for producing the same, and aqueous dispersion and ink jet ink using the same
CN101080268A (en) Process for preparing an encapsulated particulate solid
CN1194054C (en) Printing ink containing water and its use
CN1088597A (en) Comprise the dye mixture that has from the azoic dyestuff of the coupling component of diamino-pyridine series
CN100340619C (en) Acidic mono azo dyestuffs
CN1051346C (en) Ink-jet printing cloth, ink-jet printing process, and print
CN1347943A (en) Printing ink, ink jet recording process, recording product, recording unit, ink box, ink jet recording device, auxoflorence method and fluorescence prolonging
CN1494829A (en) Antimicrobial additive and ink composition containing said additive
CN1966853A (en) Use of active dye as ink-jet printing ink
CN1205282C (en) Alkoxy silicane binder used as accessory ingredient in spraying ink
CN1296443C (en) Ink for ink injection record and ink box with the said ink and recording device
CN100347244C (en) Mono azo dyes
CN1646641A (en) Composition for printing recording materials
CN100338097C (en) Polyuronic acid derivative and aqueous ink composition comprising polyuronic acid derivative
CN1863878A (en) Aqueous pigment dispersion for inkjet ink and inkjet ink composition
CN100349995C (en) Alkali ink composite

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CX01 Expiry of patent term
CX01 Expiry of patent term

Granted publication date: 20080806